Catalytic conversion of hydrocarbons



CONDENSEIR s. c. cARNEY CATALYTIC CONVERSION OF HYDROCARBONS Filed Nov. 13,"194'5 sept. 24, 1946.

J OISEDD L E mozozbL m lv GI N R A 9 l mo M L x Rf T w 2 5 DL un a mw DN RN E O E0 OR N 2 WM TC mozoFE m 5 R mozoCu... wm. T E NO VC. T 4 L m m wm ms A |1 2 E t. NY W l. UH 6 92.523? NU O zoFoL M r u N l ANH E D w MR 5 4/ 4./ EJO m mm F P lv Po m5, o A m m a c 2 7, lllllllllllll C 5 4 m mmwmmom? 4 o\ F 1 E 6 4. 5 B 4K' A 6 4 G 5 R N l H m 555m m ME 7 .Plv RD. Um R 6 3 L TA WR l' *E T 4 4 SV Mo N UL m Y T O LH 6 3 U N N 4 N AC l L B O A OO A! M L RBD N n O DRE 2 A c Il Patented Sept. 21.4, 1946 Y' UNITEDfsTATEs PATENT OFFICE -CATALYTIC CONVERSION F ZHYDROCARBONS Samuel C. Carney, Bartlesville, Okla., assigner to Phillips Petroleum C l Delaware ompany, a corporation of Application November 13, 1943, Serial No. 510,179

` is .assuming increasing importance iin. petroleum refining operations. The isomerization yof the normal paraflins to .isoparaflinsfA is carried out ,commerciallyuwith varying` :degrees of success. Aluminum halides, particularly aluminum chloride, are among the mostV promising catalysts for these reactions. In carryingout isomerization of paraflins in the presence' of aluminum vchloride the parafns are contactedinl liquid or` vapor phase vwith aluminumv chloride inthe presence of hydrogen chloride as a promoter. General practice is to use the aluminum chloride insolid form, usually admixed with or Adeposited* on a suitable carrier material.Y Carrier materials may be coated with aluminum chloride by mechanical mixing, by fusion of. the aluminum chloride with the carrier, by impregnating the: carrier under pressure with. molten aluminum chloride, and by sublimation oftaluminum chlorideonto the carrier. Alternatively, the .aluminum vchloride may ber-used in finely divided 'formrsuspended inA an inert liquid; in liquid phase, particularly in vtheform of the double salt o faluminum chloride with other metal chlorides; orein the vapor phase.-y f

Although aluminum chloride is a well known catalyst for a widevariety of reactions other than isomerization, and has long been used as a cracking catalyst'certain problems of operation re-` sulting from Vthe physical and chemical properties'of aluminum chloride have never been` Vsatisfactorily, solved. Aluminum vchloride hasgslight, but definite, solubility in hydrocarbons., It also possesses VAsubstantial volatility at the tempera- .tures required'fcr hydrocarbon conversion. Due

9 Claims. (Cl. E60-683.5)

.Y Aluminum chloride reacts with certain hydrocarbons, which may be present in the feed stream vor formedV in the reactor, forming an undesirable liquid `sludge of low catalytic activity. The sludge tends to form a coating over the solid aluminum chloride preventing contact with the hydrocar-v bons. Sludge formationv represents'a loss of aluminum chloride catalyst. Replenishing the aluminum chloride lost by sludge formation. is

costly andthe sludge itselfis a nuisance in that` it creates a disposal problem.

"The idealV solid `catalyst is onejwhich Willre-v lmain in solid form-under the conditions at which Y the y.catalyzed reaction takes place so that feed materia] may be passed in either liquid or vapor phase Lover an extended surface of vthe catalyst. 'llfleldeall catalyst should be selective in itsaction, promoting only the desired reaction, and should not react with eitherthe' feed stream or the reaction products. 'From a consideration of thefphysiclal, chemical, andcatalytic yproperties oflaluminum chloride,v itis evident that. it is far yfrom ideal as a lsolid catalyst in spite of its vhigh catalytic activity.

As` mightY be expected, many attempts .have been `.made to devise ay mechanical system for carrying out the isomerization processwith aluminum chloride whichV would take into consideration the undesirable physical and chemical properties of this catalyst. l

[Generally speaking, catalytic operations may be'clas'sied inthe following groups with respect to the'phaserelationship of catalyst and reactants. v

..1-.y Catalyst and feed in a single liquid phase.

` Vv2. Catalyst and feed both in vapor phase.

to the solubility in hydrocarbons'some aluminum I3. ACatalyst in solid. phase, feed in liquid or vapor phase.- f

4. Catalyst in liquid'phaSe, either as such or in solution; Yfeed in vapor phase or in a second liquid phase 1 v5. Catalyst in vapor phase, feed in liquid phase.

VIn groups l and 2 the catalyst and reactants arev inV the. mostv intimateV contact. Operations falling Within either groups land 2 present desirable operating conditions vbecause of the nature of the contact between the Acatalyst and the reactants; Processes of the typey classed in grouppl depend for operation upon complete miscibilty ofcatalyst and reactants. Since vapors are fully miscible, operation of a process inv accordance with group 2 may generally ybe more subsequently regenerated by heating the aluminum chloride-antimony trichloride mixture which effects vaporization of aluminum chloride thereu from. The antimony trichloride, in turn,A .is reused for absorption of aluminum chloride vapors. The mutual solubility of aluminum chloride and antimony trichloride is known'. It is also known that antimony trichloride acts as appromoter for aluminum chloride in iscmerlzation 4 drocarbon vapors. In the preferred modication of this invention the still A, reactor B, and absorber C are parts o'fthe same column as illustrated and described herein. It will be evident to those skilled in the art that these Zones may be separated orotherwise arranged While still maintaining the functions of these elements as described herein. Each of sections A, B, and C isof suitable size to eiect the desired operation, section B being generally larger than sections A or C to provide the necessary residence time required to allow the reaction to take place to the ,l desired extent.

of parains. The present invention utilizes anti-` mony trichloride in hydrocarbon conversion reactions in a new and useful manner.

The advantages of operating in accordance with the present invention with catalyst and reactants in vapor phase are:

1. Solid aluminum chloride with its attendant disadvantages is not present in the reactor.

2. Perfect contact of catalyst and hydrocarbon While both are in Vapor phase is attained in the reactor.

3. Coating of catalyst with sludge is eliminated.

` 4. The process may be operated continuously without necessity of interruptions to replace catalyst. y y Y l An object of this invention is to provide an improved process for the conversion of hydrocarbons in the presence of a metal halide catalyst.

Another object of this invention is to provide an improved process for the isomerization of normal paraffins to isoparaflins.

Still another object of this invention is to provide such a process wherein parafns are isomerized in the presence of a metallic halide catalyst wherein the catalyst and reactants are in Vapor phase.

A further object of this invention is to provide an improved process for the vapor phase isomerization of normal butane to isobutane inthe I presence of vaporous aluminum chloride as a catalyst. A still further object of this invention is to provide a process for the separation of aluminum chloride vapors from hydrocarbon vapors byfab sorption with antimony trichloride. Further objects and advantages of this invention will be evident from the following detailed description of specific applications of the invention and the accompanying drawing illustrating diagrammatically the described specific embodiments. f y

Figure 1 illustrates diagrammatically apparatus suitable for carrying out paraflin isomerization by the process of this invention.

Figure 2 illustrates diagrammatically apparatus suitable for a more general application` of the process of the present invention to hydrocarbon conversion.

' With reference to Fig. 1 of the drawing, the numeral l designates a column of suitable size divided into three sections, A, B, and C. section- A constitutes a still in which aluminum chloride is vaporized.l Section B is the reaction chamber in which reaction of the hydrocarbon takes place in vapor phase in the presence of aluminum chloride vapors. Section C is an absorber in which aluminum chloride vapors are separated frornhy- Hydrocarbon `feed, normal butane for isomerization to isobutane', enters through line 2. The major portion of the feed passes to heater 3 wherein the'nor'mal butane is heated to the operating temperature, and from which the vapors may be passed through valve 4 into the reaction sectonB or through valve 5 to the distributor 6 in the lower part of the still A. The normal bu.- tane thus introduced contacts vapors of aluminum chloride and hydrogen chloride in vapor phase in the reactor where isomerization of normal butane to isobutane takes place.

The temperature in the reaction zone is above the vaporization temperatureof aluminum chloride and below the temperature at which u ndesirable reactions take place. Aluminum chloride sublimes at a temperature of about 178 C'. and has a boiling point of about 183 C. at atmospheric pressure; At 21/2 atmospheres pressure the boiling point of aluminum chloride is about 190 C. Accordingly, the temperature in the reaction'chamber maybe within about 190 C. to about 250 C. Preferably the temperature within the reactor is coniined within the limits of about` 190 C. to about 220 C. The isomerization of normal .butane to isobutane is exothermic, hence there is a tendency for the temperature to increase from the bottom to the top of section B. The temperature in section B may be controlled by injection of normal butane at one or more points along the length of the reaction chamber. The temperature at the top of the reaction chamber B is limited to a value below about 200 C. by the addition of fresh normal butane, preferably in liquid form to take advantage of the heat of vaporization. For this purpose, a part of the normal butane from line `l is passed through line 1 to a distributor 8 in the reaction chamber B.

Vapors from the reaction chamber, comprising hydrocarbons, hydrogen chloride, aluminum chloride, and antimony trichloride vapors, pass through the chimney 9 into the absorber C. The absorberC is provided with vapor-liquid contact means, as,` for example, packing or bubble plates. In the absorber the vapors from the reaction chamber are brought into contact with liquid antimony trichloride. The temperature in the absorption section is preferably within the range of C. to about 200 C. The antimony trichloride absorbs aluminum chloride vapors from the hydrocarbon stream. The mixture of aluminum chloride and antimony trichloride hows from the absorber C through the downspout I0 to the vaporizer or still A. Still A preferably is provided with plates or packing providing vapor-liquid Contact means similar ot that of the absorber. Heat is supplied to the still by suitable heating means, e. g., steam coil. In the still the aluminum ychloride is liberated from the antimony trichloride and passes up into the reactor B. The hydrocarbon vapor'supplied tothe still from the distributor 6 aids in the vaporization of the alumin'um 'chlorideby its 'stripping action.v audits eiecton .thel partialnpressures in the still., The temperature in the stillV is maintained within the range ofxabout 180 C..toV about'220 C'. t

Liquid .antimony trichloride is.v drawn from the stilland passed bypump l2 to the cooler I3;V The cooleryl may conveniently be cooled by boi-ling water'to` obtain a temperature approaching 100 C. In any case the antimony trichloride isnot cooled below about 80 C. since-it solidiiies at '1 31.4 C. The cooled antimony trichloride isi ythen passed through line I4 to the upper part of the absorber C for further absorption of` aluminum chloride vapors, thereby'completing its cycle. A part of the stream from theabsorber Cfmay be passed via line l5 to a-catalyst make-,up chamber l5. Inchamber I6 fresh aluminum .chloride is added, as needed, andpasses in solution in the antimonyl trichloride from the absorber to the still A through line I1.

The hydrocarbonvapors, lfreed from aluminum chloride vapors, leave the column by line and passito the condenser 2| g Condensate is collected` inA the accumulator.k 22 and fed via line` 24 to the fractionator 25. The fractionator 25 is provided with suitable refluxing and reboiling means as is customary. Hydrogen chloride is separated from' the hydrocarbons and returned to column I via line 2,0. Additional hydrogen chloride may be supplied as needed through line 21. Fromvfractionator 25, thev hydrocarbons are passed through line- 2,8 to. the fractionator 29 in 7 num` `chloride Sludgeof Aabout 50 C. to about 250 C.; cracking', generally at temperatures above about 250 C. It willbe recognized by thosek skilled in the art thatV the composition of the feed and other operating conditions` aiect the reaction and govern the tem'- perature at which a given reaction'is best' carried out. The temperature in the reactor is immaterial to the operation of this modification of the present invention, it being essential only that the temperature of the vapors entering the absorber d1 be within. the range of about '15 C. to about 200 C.

In the absorber 41, the hydrocarbon vapors containing vaporous aluminum chloride are contacted with liquid antimony trichloride which effects solution ofthe aluminum chloride vapors. Fresh antimony trichloride may be added tothe absorber and saturated antimony trichloride, re-

moved from theY absorberas required, e. g.,in

Which'the-isobutane is lseparated from unreacted t j normalbutane. The isobutane passes overhead throughline 30; normal butane is returned recycle for throughfline 3f! to theheater 3- as conversion to isobutane.

The foregoing detailed description is specic to Y the isomerization of normal-butane to isobutane in the presence of aluminum chloride as catalyst using hydrogen chloride as promoter for the reaction. Itis to be understood that inthe process of the present invention, normal parafns other than butane may be employed as feed tothe isomerization reaction. The aluminum chloride is promoted by a hydrogen halide, generally hydrogen chloride is employed because of its availability. It is well knownrthat other metal halides catalyze the isomeriaationreaction and that these catalysts may be promoted by hydrogen halides. Aluminum bromide is known to be a goodrisomerization catalyst which may befpromotedby hydrogen bromide. It is also known to use mixtures of aluminum chloride and aluminum bromide as catalysts for this reaction. l

`Figure 2 of the drawing illustrates inra more generalwa-y the application of the present invention to hydrocarbon conversion processes in which an aluminum chloride catalyst is used. Cracking, isomerization, orother-reaction promoted by aluminum chloride may be carried out in the apparatus illustrated. Reaction takes place inthe reactor 4u in the presence of aluminum chloride as catalyst and-hydrogen chloride as promoter. The ,aluminum chlorideis preferably present in the reactor in vapor phase; it Will be evident, however, thatV aluminum chloride maybe present in the reactor Ain liquid or .vaporr phaseL The hydrocarbon feed enters the reactor through line 42. A suitable coolant, preferably hydrocarbons, may Vbe added to the reactor through line 43 as the V,manner described inconnection'with Fig. 1 by means of, lines 63 and 64, respectively. Thefabsorbed. aluminumchloride is subsequently vaporize'd from the. antimony trichloride Iin the vaporizer 48 and returned to the reactor 40. through line 45. The vaporizer 48 is provided with heating means 49 and means 50 for admitting stripping vapor .thereto to 'effect Vaporization of aluminumchloride. It will be evident to rone skilled inthe art that the.. absorber and vaporizer may be so constructed asto be interchangeable, each serving alternately asfabsorber and vaporizer.

Hydrocarbon vapors freed of aluminum chlorideare passed from the absorber 41 to the condenser 52. Condensate from the condenser collects in accumulator 54 from which it is passed tothe fractionator' 55. `The promoter is'separated from thehydrocarbons and returned to the reactor through -line 51; additional promoter may be added as requiredthrough-line 58. The hydrocarbons are passed fromthe fractionator. 56 to a second fractionator 60 for separation of product from unreactedhydrocarbons. The desired product leaves the fractionator by line 6|; unreacted hydrocarbons kare returned to the reactor 40 through line 62. f

Antimony trichloride is liquid at atmospheric pressure at temperatures within the range of about-'14 C. to about 220 C, This liquid is readily transferred from point topoint in the system. While; aluminum chloride is solid atV temperatures below aboutg180` C; it should be noted that it has va definite vapor pressure at temperatures below'its melting point. The vapor pressuresV of desired. The aluminum chloride is charged to Y( thereactor in any convenient manner; it may be Aadmitted through line 42 or line 43 if desired.

Liquid hydrocarbons, togetherwith `anya1umi-` aluminum chloridel atv various temperatures are approximately as follows In view of the fact thathydrocarbon vapors are present in large quantities in the reactor, it will be readily appreciated that large quantities of aluminum chloride vapors appear in the hydrocarbon vapors even When using solid aluminum chloride at temperatures below the vaporization temperature. The present invention has Wide application in the removal of aluminum chloride vapors from hydrocarbon vapors in the eiliuents of hydrocarbon conversion processes in which aluminum chloride is used as catalyst.

I claim:

1. A process for the conversion of hydrocarbons in a reaction catalyzed by aluminum chloride which comprises contacting the` hydrocarbon With aluminum chloride in a reaction zone under conditions such that the desired reaction is effected, passing vaporous eiiluent from the reaction zone containing hydrocarbon vapors and aluminum chloride vapors into contact with liquid antimony trichloride effecting separation of aluminum chlon ride vapors from the hydrocarbon vapors by solution in liquid antimony trichloride, subsequently liberating aluminum chloride vapors from liquid antimony trichloride, and returning the aluminum chloride to the reaction zone as catalyst.

2. In a process for conversion of hydrocarbons in a reaction catalyzed by aluminum chloride, the

improvementY which comprises contacting vaporous` eiliuents of the reaction containing aluminum chloride vapors in admixture with hydrocarbon vapors With liquid antimony trichloride eiecting separation of aluminum chloride vapors from the hydrocarbon vapors by solution in liquid antimony trichloride, and subsequently liberating aluminum chloride vapors from liquid antimony trichloride.

3. In a process for the conversion of hydrocarbons in a reaction catalyzed by aluminum chloride, the improvement which consists in contacting vaporous eluents of the reaction containing aluminum chloride vapors and hydrocarbon vapors With liquid antimony trichloride effecting separation of aluminum chloride vapors from the hydrocarbon vapors by solution in liquid antimony trichloride.

4. A process for the conversion of hydrocarbons in a reaction catalyzed by aluminum chloride which comprises contacting the hydrocarbons with aluminum chloride in a reaction zone, passing vaporous eiiluent from the reaction zone containing aluminum chloride vapors to an absorption zone into contact with liquid antimony trichloride at a temperature in the range of about 75 C. to about 200 C. effecting removal of aluminum chloride from said hydrocarbon vapors by solution in liquid antimony trichloride, passing antimony trichloride containing aluminum chloridein solution therein from the absorption zone to a distillation zone, liberating aluminum chloride from antimony trichloride in the distillation zone by heating to a temperature within the range of about 180 C. to about 220 CL, and passing the liberated aluminum chloride vapors from the distillation zone to the reaction zone.

5. The process of isomerizing a normal paraffin to the corresponding isoparafn Which comprises intimately contacting the normal paraffin in vapor phase with volatilized aluminum chloride as a catalyst in the presence of an anhydrous hydrogen halide promoter in a reaction zonesub-V stantially free from liquid phase and for a period of time such as to effect isomerization to the isoparain, removing the resulting mixture in vapor state from said reaction zone and scrubbing it Witli molten antimony trichloridein an absorbing zone and thereby .dissolving aluminum chloride from said mixture in said molten antimony trlchloride while allowing the resulting vaporous mixture of unconverted normal paran, isopara'in and hydrogen halide to pass through undissolved, passing the resulting solution of aluminum chloride in antimony trichloride to a stripping zone and there stripping the dissolved aluminum chloride in vaporous form therefrom, and passing the resulting vaporous aluminum chloride into said reaction zone. f

6.' A process for the vapor-phase isomerization of normal parains to isoparafns in the presence of aluminum chloride which comprises contacting vapors of a normal paraiiin with aluminum chloride vapors in the presence of hydrogen chloride at a temperature within the range of about 190 C. to about 250 C. in a reaction zone in the absence of liquid phase; passing vaporous eilluent of said reaction zone containing vapors of aluminum chloride, hydrogen chloride, normal parain and isoparaflin into intimate contact with molten antimony trichloride at a temperature Within the range of about 180 C. to about 200 C. in an absorption zone thereby dissolving aluminum chloride from said vapors while allowing the hydrogen chloride, normal paraffin and isoparafn vapors to pass through undissolved; passing the resulting solution of aluminum chloride in antimony trichloride to a distillation zone and liberating the aluminum chloride from the antimony trichloride in said zone at a temperature Within the range of about 180 C. to about 220 C. in the presence of hydrocarbon vapors as stripping medium; and passing aluminumv chloride vapors from the distillation zone to said reaction zone.

7. The process of claim 6 in which said normal paraffin is normal butane and said isoparaflln is isobutane. Y

8. A process for isomerization of normal parailins to isoparafns which comprises contacting said normal' parain with aluminum chloride in a reaction zone in the presence of hydrogen halide and at a temperature within the range of'about 50 C. to about 250 C. effecting isomerization of normal paraffin to isoparafn, passing vaporous eflluent of said reaction zone to an absorption zone into intimate contact with liquid antimony trichloride at a temperature Within the range of about 75 C. to about 200 C. effecting selective solution of aluminum chloride vapors contained therein, passing the solution of aluminum chloride in antimony trichloride to a distillation zone and vaporizing aluminum chloride from antimony trichloride in said zone at a temperature in the range of about 180 C. to about 220 C.; and passing aluminum chloride thus liberated in the distillation zone to the reaction zone.

9. A process for the vapor-phase isomerization of normal butane to isobutane which comprises passing vaporous-normal butane into a body of liquid antimony trichloride having aluminum chloride dissolved therein and maintained at a temperature adequate to vaporize said aluminum chloride therefrom, passing resulting vapors of normal butane and aluminum chloride upwardly into and through a separate reaction zone disposed above said body of liquid and maintained at isomerization conditions of temperature and pressure and substantiallyfree from liquid phase, said reaction zone being of sufcient size to eiect substantial vapor-phase isomerization therein, passing resulting vapors of normal butane, isobutane and aluminum chloride upwardly into and through a separate scrubbing zone disposed above said reaction zone, contacting the last-mentioned vapors in said scrubbing zone with liquid antimony triohloride to dissolve substantially all of the A1013 from said vapors, recovering from said scrubbing zone vapors comprising isobutane substantially free from aluminum chloride, owing resulting solution of aluminum chloride in liquid antimony 10 trichloride by gravity to said body of liquid antimony trichloride through a path separate from Y said reaction zone, and passing liquid antimony trichloride from said body of liquid antimony trichloride to said scrubbing zone for use therein 

